The v(6)=2 States of the Four C(3v)-Symmetry Isotopomers of FClO(3).

High-resolution infrared spectra of the four isotopomers of FClO(3) of C(3v) symmetry have been analyzed in order to obtain data on overtones of the nu(6) vibrational mode. For v(6)=2, two different approaches have been used. The component with l(6)=0 has been studied by the analysis of the 2nu(6)(0) parallel band at 809 cm(-1) and 779 cm(-1) for the species with (16)O and (18)O respectively. But since the 2nu(6)(-/+2) perpendicular band is too weak to be observed, the component with l(6)=+/-2 was reached through the hot band 2nu(6)(+/-2)-nu(6)(+/-1). Thereafter, the energies of the v(6)=2, l(6)=0, +/-2 states were fitted to three slightly different models. The molecular parameters obtained are highly consistent, not only between the two components, but also with v(6)=1 and moreover from one isotopomer to the other. This work is supplemented by a short vibrational analysis of the parallel hot bands 3nu(6)-2nu(6), 4nu(6)-3nu(6), 5nu(6)-4nu(6), and 6nu(6)-5nu(6) which form a regular sequence. Copyright 2001 Academic Press.

Rovibrational and Rotational Spectroscopy of Levels of Propyne around 1000 cm(-1).

Four vibrational levels in the energy region around 1000 cm(-1) were studied. These were the v(5)=1 and v(8)=1 fundamental levels, both components of the v(9)=v(10)=1 combination level (l(9)=l(10)=+/-1 and l(9)=-l(10)=+/-1), and both components of the v(10)=3 overtone level (l(10)=+/-1 and +/-3). New FTIR spectra with a synchrotron radiation source were recorded in the region of the "superhot" v(10)=3<--2 bands, which made possible the first assignment of levels of the v(10)=3(+/-1) sublevel. More than 330 new rotational transitions in the combination and overtone levels were measured by millimeter-wave spectroscopy betwen 50 and 360 GHz. The new data were analyzed simultaneously together with the previously assigned rovibrational data for the fundamental and combination levels and rotational data for the fundamental levels using a global model with all anharmonic, Coriolis, l-type, and alpha-resonances. Significant improvement of data reproduction and very good consistency with the Hamiltonian parameters of the lower vibrational levels v(9)=1 and v(10)=1, 2 were achieved. A strong dependence of the A(v) constant on the l(10) quantum number is found for propyne: this is shown to be characteristic of skeleton C-C identical withC or C-C identical withN bending modes in H(3)CCCH, H(3)CCN, and their fully deuterated species. Copyright 2001 Academic Press.

The myrosinase-glucosinolate system in the interaction between Leptosphaeria maculans and Brassica napus.

summary Leptosphaeria maculans causes blackleg disease, and resistance to this fungal pathogen is an important trait in the breeding of oilseed rape. A better comprehension of the role of the myrosinase-glucosinolate system in this context is of great value. The present study is the first to address effects on multiple components of this complex system, including concentrations of individual glucosinolates, product formation, myrosinase isoform distribution and activity, and levels of myrosinase binding proteins during the infection process. One resistant B. napus cultivar (Maluka) and one susceptible cultivar (Westar) were compared in the investigation. Our results show that the two cultivars had the same histological distribution, isoform expression, and activity of the myrosinase enzymes. The glucosinolate levels were also similar, with the exception of glucobrassicin and neoglucobrassicin, which were significantly lower in the resistant cultivar at 11 days post-infection. Growth of the fungus on the plant tissues did not alter glucosinolate levels, suggesting that L. maculans does not degrade these compounds. When the plants were starved of sulphur, and thereby depleted of glucosinolates, no increased susceptibility was observed. Hence, we suggest that the myrosinase-glucosinolate system does not determine the outcome of the interaction between B. napus and L. maculans.

High-Resolution Spectrum and Rovibrational Analysis of the nu(2)/nu(5) Dyad of D(3)SiF near 700 cm(-1).

The nu(2) (A(1), 710.157 cm(-1)) and nu(5) (E, 701.717 cm(-1)) fundamental bands of D(3)(28)SiF have been studied by FTIR spectroscopy with a resolution of 2.4 x 10(-3) cm(-1). We assigned 1648 lines for the parallel band (J(max) = 50, K(max) = 21), 4279 for the perpendicular band (J(max) = 52, K(max) = 27), and in addition 671 perturbation-allowed transitions (J(max) = 50, K(max) = 12). The nearly degenerate v(2) = 1 and v(5) = 1 states are linked by (DeltaK = +/-1, Deltal = +/-1) and (DeltaK = +/-2, Deltal = -/+1) interactions, while the l(5) = +/-1 levels of nu(5) interact also by l(2, -1), l(2, 2), and l(2, -4) interactions. The first model with 36 free parameters, taking into account all these resonances through a nonlinear least-squares program, gave standard deviations of 1.56 x 10(-4) cm(-1) for 5997 nonzero-weighted IR data and 138 kHz for 8 MW data from the literature. The second model, in which the main Coriolis term was constrained to a force field value, used 37 parameters and gave similar standard deviations. A new determination of the A(0) and D(0)(K) ground state parameters was performed by two methods: either using differences between "forbidden" transitions differing by 3 in K or letting A(0) and D(0)(K) free in the global fit. The values obtained are fully compatible with those obtained previously by the "loop method." Copyright 2000 Academic Press.

The Mystery of a Band Vanishing upon Isotopic Substitution: The Case of the v(3) = 1 State of FClO(3).

F. Meguellati, G. Graner, K. Burczyk, and H. Bürger [J. Mol. Spectrosc. 185, 392-402 (1997)] reported in their paper on nu(3)(A(1)) bands of the (35,37)Cl and (16,18)O isotopomers of FClO(3) that the nu(3) bands, which, although weak, could be well observed for the (16)O isotopomers, disappear almost completely in the spectra of the (18)O isotopomers. Because the A and B values for the (18)O isotopomers are so similar that these molecules are very close to spherical tops, much closer than the values for the (16)O species, disappearance of the band was ascribed to selection rules for tetrahedral molecules, the A(1) vibrations of which are inactive. Alternative explanations are proposed in this paper and analyzed. The most likely explanation is that a coincidence among the intensity parameters is responsible for a very low value of the dipole moment derivative; a weak Fermi resonance with the (v(6) = 2, l = 0) state may also participate in the final total wipeout of the band. It is believed that the last mechanism may be of more general interest. Copyright 2000 Academic Press.

High-Resolution Absorption Spectroscopy of the 3nu(1) and 3nu(1) + nu(3) Bands of Propyne.

The 3nu(1) and 3nu(1) + nu(3) bands of propyne have been recorded at Doppler-limited resolution by Fourier transform spectroscopy and intracavity laser absorption spectroscopy, respectively. The two bands show a mostly unperturbed J rotational structure for each individual K subband. However, as a rule the K structure ordering is perturbed in overtone transitions of propyne and different effective parameters associated with each K subband have been determined. From the vibrational energy levels, a value of -6.6 cm(-1) has been obtained for the x(13) cross anharmonicity in perfect agreement with the origins of the nu(1) + nu(3) and 2nu(1) + nu(3) combination bands estimated from the FTIR spectrum. Hot bands from the v(9) = 1 and v(10) = 1 levels associated with the 3nu(1) + nu(3) combination band have been partly rotationally analyzed and the retrieved values of x(39) and x(3,10) are in good agreement with literature values. Finally, the 4nu(1) + nu(9) - nu(9) band centered at 12 636.6 cm(-1) has been recorded by ICLAS. The red shift of this hot band relative to 4nu(1) and the DeltaB(v) value are discussed in relation to the anharmonic interaction between the 4nu(1) and 3nu(1) + nu(3) + nu(5) levels. Copyright 2000 Academic Press.

Rovibrational Analysis of the nu(6) Bands of Four Symmetric Isotopomers of FClO(3).

High-resolution (ca. 5 x 10(-3) cm(-1)) infrared spectra of monoisotopic samples of F(35)Cl(16)O(3), F(37)Cl(16)O(3), F(35)Cl(18)O(3), and F(37)Cl(18)O(3) have been recorded in the region of the nu(6) fundamental band. This band is centered at 405.6055, 405.5097, 390.5406, and 390.4984 cm(-1), respectively. About 1000 nonzero-weighted transitions were fitted for each isotopomer with an isolated band model, obtaining a s.d. on the residuals close to the experimental precision. Three different reductions of the Hamiltonian have been tested and found almost equally good, although FClO(3) is a nearly spherical top molecule. Each includes the l(2, 2) interaction and either a d(t) DeltaK = +/-3 interaction term (reduction Q) an epsilon(t) DeltaK = +/-3 interaction term (reduction QD), or an l(2, -1) interaction (reduction D). Good agreement between the theoretical predictions for these reductions and the experimental data is observed. Copyright 1999 Academic Press.

H(3)Si(37)Cl Revisited with High Resolution: The Ground State and the v(2) = 1; v(3) = 1, 2, and 3; v(5) = 1; v(6) = 1 and 2; and v(3) = v(6) = 1 States.

The infrared spectrum in the range 400-1600 cm(-1) of isotopically pure H(3)Si(37)Cl has been recorded at high resolution (2.4-6.6 x 10(-3) cm(-1)) and analyzed. Fifteen bands have been studied, namely the four fundamentals nu(3) (543.968 cm(-1)), nu(6) (663.738 cm(-1)), nu(2) (947.982 cm(-1)), and nu(5) (950.657 cm(-1)), the overtone bands 2nu(3), 2nu(0)(6), and 2nu(-/+2)(6), the combination band nu(3) + nu(6), and seven hot bands. Improved ground state constant parameters have been obtained, including all four sextic distortion constants. As for the J-independent parameters A(0), D(0)(K), and H(0)(K), they were determined mainly through the "loop method" involving nu(6), 2nu(-/+2)(6), and 2nu(-/+2)(6)-nu(+/-1)(6) and checked through the strong interactions between nu(2) and nu(5), producing some "forbidden lines." The nu(2)/nu(5) dyad was fitted with success using two different reduced Hamiltonians. Concerning nu(3) and nu(6), in spite of their relatively large separation, a Coriolis interaction could be evidenced. In both nu(2)/nu(5) and nu(3)/nu(6) interacting systems the sign of the interaction was found positive. As for the overtones, 2nu(3) was treated as isolated and 2nu(0)(6) and 2nu(-/+2)(6) as linked together by an l(2, 2) interaction. The data on the v(3) = v(6) = 1 levels were obtained mainly from the two hot bands nu(3) + nu(6) - nu(3) and nu(3) + nu(6) - nu(6), and marginally from the weak band nu(3) + nu(6), and also fitted as for an isolated level. A weak x,y-Coriolis interaction with level crossing between K/(kl - 1) = 21 and 22, and a local l(1, -2) resonance at K = 13/kl = -15 between 2nu(3) and nu(5) were furthermore detected. Copyright 1999 Academic Press.

The Interacting v6 = 2 Levels of D3Si35Cl: A Tool to Determine Ground State Constants from High-Resolution Spectra in the 440-590 and 900-1100 cm-1 Regions.

High-resolution FTIR spectra of monoisotopic D3Si35Cl have been recorded in the regions 440-590 cm-1 (nu3/nu6) and 900-1100 cm-1 (2nu6/nu3 + nu6/2nu3). A detailed rovibrational study was done for the 2nu06, 2nu-/+26, and 2nu3 overtone bands and for the 2nu+/-26-nu+/-16, 2nu06-nu-/+16, and (nu3 + nu+/-16)-nu+/-16 hot bands. For the first time the interactions occurring between the v6 = 2, v3 = v6 = 1, and v3 = 2 levels of any trideuterated silyl halide have been analyzed. The (nu3 + nu+/-16)-nu+/-16 hot band served to obtain accurate energies of the v3 = v6 = 1 level, the nu3 + nu6 combination band not being detectable on our spectra. The first experimental determination of A0 and D0K for this molecule was undertaken by a well-established method, using the nu6, 2nu+/-26-nu+/-16, and 2nu-/+26 bands. Ground state energy differences DeltaK(J) = E0(J, K) - E0(J, K - 3) were calculated for K values from 2 to 16. By a least-squares fit of 163 such differences, the A0 and D0K values thus obtained were (in cm-1): A0 = 1.4278230(8) and D0K = 5.3916(31) x 10(-6). Copyright 1999 Academic Press.

High-Resolution Study of the First Stretching Overtones of H3Si79Br.

The Fourier transform infrared spectrum of monoisotopic H3Si79Br (resolution 7.7 x 10(-3) cm-1) was studied from 4200 to 4520 cm-1, in the region of the first overtones of the Si-H stretching vibration. The investigation of the spectrum revealed the presence of two band systems, the first consisting of one parallel (nu0 = 4340.2002 cm-1) and one perpendicular (nu0 = 4342.1432 cm-1) strong component, and the second of one parallel (nu0 = 4405.789 cm-1) and one perpendicular (nu0 = 4416.233 cm-1) weak component. The rovibrational analysis shows strong local perturbations for both strong and weak systems. Seven hundred eighty-one nonzero-weighted transitions belonging to the strong system [the (200) manifold in the local mode picture] were fitted to a simple model involving a perpendicular component interacting by a weak Coriolis resonance with a parallel component. The most severely perturbed transitions (whose ||obs-calc || values exceeded 3 x 10(-3) cm-1) were given zero weights. The standard deviations of the fit were 1.0 x 10(-3) and 0.69 x 10(-3) cm-1 for the parallel and the perpendicular components, respectively. The weak band system, severely perturbed by many "dark" perturbers, was fitted to a model involving one parallel and one perpendicular band, connected by a Coriolis-type resonance. The K" . DeltaK = +10 to +18 subbands of the perpendicular component, which showed very high observed - calculated values ( approximately 0.5 cm-1), were excluded from this calculation. The standard deviations of the fit were 11 x 10(-3) and 13 x 10(-3) cm-1 for the parallel and the perpendicular components, respectively. Copyright 1998 Academic Press.

High-Resolution Infrared Spectrum of H3SiI in the nu1/nu4 Region near 2200 cm-1

The Fourier transform infrared spectrum of H3SiI has been recorded in the nu1/nu4 region from 2075 to 2315 cm-1 at an optical resolution of 2.3 x 10(-3) cm-1. The nu1/nu4 fundamental bands and the (nu1 + nu3) - nu3/(nu4 + nu3) - nu3 hot bands have been rotationally investigated. Numerous local perturbations have been observed in the nu1 and nu4 bands and in the hot bands. Without the lines involved in perturbations, more than 2900 transitions of the nu1/nu4 bands were used to determine the band origins and the vibration-rotation parameters of the nu1 = 1 and nuv4 = 1 states. A least-squares fit of 766 apparently unperturbed transitions of the hot bands gave the parameters of the nu1 = nu3 = 1 and nu4 = nu3 = 1 states. The l(2, 2) resonance in nu4 and the A1-E Coriolis coupling between nu1 and nu4 have been investigated. Most of the local perturbations have been studied individually using a simple model by which the main perturber for each resonance was identified. Copyright 1998 Academic Press.

The First Si-H Stretching Overtone of H3SiD: Emergence of Local Mode Effects

The FTIR spectrum of H3SiD in the 4100-4500-cm-1 region was recorded at Doppler-limited resolution, and four bands were studied. At lower wavenumbers, two strong bands, which in the local mode picture can be assigned to (200, E) (nu0 = 4308.5667 cm-1) and (200, A1) (nu0 = 4307.8441 cm-1), were analyzed, and at higher wavenumbers, two weaker bands, namely (110, E) at 4378.1950 cm-1 and (110, A1) at 4375.9763 cm-1, were analyzed. A total number of approximately 1900 lines in the strong dyad and 1000 lines in the weak one were assigned and fitted with standard deviations of the residuals approximately 0.0008 cm-1. The strong system (200) is close to local mode behavior, with no x, y Coriolis term needed and only a small z Coriolis term, and simple arithmetic relations between vibration-rotation parameters are fulfilled as expected. The local mode behavior of the weak system (110) is less pronounced, but z and x, y Coriolis effects are smaller than in the Si-H stretching fundamentals. Comparison of computed and observed spectra provided a good estimate for the ratios of transition moments of the different bands: they are, in absolute value, proportional to 3.5:1.75:1:1 for (200, E), (200, A1), (110, E), and (110, A1), respectively. Copyright 1998 Academic Press.

Can Isotopic Substitution Change a Bright State into a Dark State? The Case of the v3 = 1 State of FClO3

High-resolution infrared spectra of monoisotopic samples of F35Cl18O3 and F37Cl18O3 have been recorded with the purpose of analyzing the nu3 fundamental at 535 cm-1. However, this band could not be observed whereas it had been seen and studied earlier in F35Cl16O3. To determine the parameters of the v3 = 1 state, indirect methods were used. Hot bands nun + nu3 - nu3 (n = 1 or 2) were first analyzed and their LSCD (Lower State Combination Differences) yielded rotational parameters of nu3. Then, with the help of nu1 + nu3, all rovibrational parameters of nu3 were obtained. Similar methods were applied to spectra of F35Cl16O3 and F37Cl16O3 to prove that the parameters of nu3 obtained in this fashion are identical to those determined directly for these isotopomers and are even more comprehensive. It is shown that the different character of nu3 in the two 18O and in the two 16O isotopomers is due to the fact that the former are much closer to a spherical top molecule ((A0 - B0)/A0 = 0.015). This is not only reflected in intensities different by two orders of magnitude but also in the very different values of alpha3B in these two pairs. Copyright 1997 Academic Press. Copyright 1997Academic Press

High-Resolution Study of the Infrared Spectrum of H3SiI in the Regions 330-680 and 1070-1360 cm-1: Accurate Determination of the Ground State Constants

High-resolution FTIR spectra of H3SiI have been recorded in the regions 330-680 cm-1 (nu3/nu6) and 1070-1360 cm-1 (2nu6). A detailed rovibrational study was carried out for the nu3 and nu6 fundamental bands, 2nu6-/+2 and 2nu60 overtone bands, and two hot bands, 2nu6+/-2 - nu6+/-1 and 2nu60 - nu6. A local resonance between the v6 = 2 and v2 = v3 = 1 states was observed. Ground state combination differences deduced from the nu3, nu6, 2nu6-/+2, and 2nu60 bands allowed us to obtain accurate B0, DJ0, and DJK0 constants. The nu6, 2nu6+/-2 - nu6+/-1, and 2nu6-/+2 bands were used for the experimental determination of the A0 and DK0 constants, whereas the hot band 2nu60 - nu6 served to make the internal calibration coherent. Ground state differences DeltaK(J) = E0(J, K) - E0(J, K - 3) were calculated with K up to 12. By a least-squares fit, we obtained the following results:A0 = 2.8426037(14) cm-1 and DK0 = 2.75840(99) x 10(-5) cm-1.Copyright 1997 Academic Press. Copyright 1997Academic Press

[Treatment and results following para-articular epiphyseal injuries of the knee during the growth period]. / Behandlung und Ergebnisse nach kniegelenknahen Epiphysen-verletzungen im Wachstumsalter.

A total of 23 children aged 3 to 18 years, underwent treatment in a period of 14 years. They were followed-up from 1 to 12 years later. The follow-up examinations confirmed that the treatment has to consider the kind of epiphyseal injury, its localisation and the patient's age in order to avoid prearthrotic deformity. Thus, conservative and operative treatment have their exact indication.

[Effectiveness of conservative treatment following distal radius epiphyses injuries]. / Die Leistungsfähigkeit der konservativen Behandlung nach distalen Radiusepiphysenverletzungen.

From 1966 to 1978, 122 infants and children suffering from injuries of the distal radial epiphysis were treated by reposition and repeated reposition. 68 of them were followed-up from 2 to 13 years later. In most cases spontaneous correction of remaining deformities by growth could be demonstrated. This remodelling of angulation depends on type and extent of the epiphyseal injury, the age of the patient and the time gone after the accident.

[Spinal column injuries in childhood (author's transl)]. / Kindliche Wirbelsäulenverletzungen.

22 children suffering from fractures and dislocations of the spinal column were seen at the Surgical Dept. of the Medical Academy of Erfurt from 1960 to 1976. This came up to 4.3% of all patients with injuries of the spine. The treatment was conservative. Vertebral fractures, without concomitant paralysis of the medulla had a favourable prognosis. In two third of the patients followed up a spontaneous compensation of deformed growth could be observed.